Process for rendering textiles water-repellent



Patented July 10, 1945 UNITED STATES PATENT orrice PROCESS FOR RENDERINGTEXTILES WATER-REPELLENT Ernst Waltmann and Edgar Wolf. Krefeld,Germany, assignors to Heberlein Patent Corporation, New York, N. Y., acorporation of New York No Drawing. Application January 3, 1938, SerialNo. 183,234. In Germany January 6, 1937 7 Claims. (CI. 8-1162) SerialNo. 177,054, filed November 29, 1937, now

Pat. No. 2,294,435, there is described the preparation of compounds fromalpha-methyl halide derivatives obtained from higher fatty acid or.naphthenic acid amides or their methylol compounds, or higher alkylamines with formaldehyde or its polymers and a halogen or hydrogenhalide; and the use of these materials for combining with textilematerials.

We have found in accordance with the hereindescribed invention that theabove-described reaction can be extended to an additional series of sprefer to employ these materials in water-soluble form and this may beeffected by employing them as their quaternary ammonium compounds.

An object of the invention, accordingly, is to provide an improvedprocess for producing waterrepellence in textiles employing materials ofthe type mentioned and to produce an improved series of water-repellenttextiles thereby.

Another object is to provide a simple process for the manufacture ofchemicals for producing such water-repellence and an improved serie ofsuch chemicals. Other objects will be in part obvious and in partpointed out hereinafter.

The invention. accordingly, consists in the novel products as well asthe novel processes and steps of processes according to which suchproducts are manufactured. the specific embodiments .of which aredescribed hereinafter by way of example and in accordance with which Inow prefer to practice the invention.

In accordance with our invention we have found that the alpha-methylhalide derivatives mentioned above may be employed either in anonaqueous solvent or in water solution. In the latter case we prefer toemploy quaternary ammonium compounds mentioned above. produced bycombining the alpha-methyl halide derivatives with pyridine.

We have found suitable for our purpose in carrying out the treatment oftextiles, the nitrogenous derivatives of higher fatty acids whichcontain a removable hydrogen atom linked to nitrogen or oxygen. Furtherthere can be employed the nitrogenous derivatives of carbon dioxidewhich contain an aliphatic radical of at least ten carbon atoms.Accordingly for example hydroxamic acids, amidines, urethanes,hydrazides, derivatives of urea or dimethylol-urea which are acylatedunilaterally with higher fatty acid chlorides, or which are acylatedunilaterally with higher fatty chlorocarbonic acidesters may beemployed. The aforesaid compounds are converted preferably by combiningthe derivatives just mentioned with trioxymethylene or formaldehyde orother polymer with a halogen material such as hydrochloric acid gas,thereby converting into methyl chloride compounds, and the latter areconverted by double decomposition with tertiary bases into water solublequaternary ammonium compounds. As methyl chloride compounds they areparticularly suitable for the etherification of cellulose or cellulosederivative fibrous material.

The processis applicable not only to cellulose,

such as cotton, or cellulose-derivative fiber material, such as thevarious forms of artificial silk, but may be also applied to animalfibers such as wool.

In the treatment of artificial silk there is secured not only awater-repelling effect, but there also is effected a diminution of thecapabilit of swelling in the presence of the swelling agents and anincrease in resistance to wetting. The effects produced on textiles inaccordance with our invention are resistant to dry cleaning and washingwith soap. A remarkable feature in all the treatments or impregnationsmade in accordance with ourinvention is the increase in wet tensilestrength of artificial silk and an increase in the fastness of the dyeson all textiles. and particularly the fastness to washing of dyedtextiles of various types including cotton, artificial silk and animalfibers. These materials resist shrinking when subjected to mildshrinking as in laundering and also more severe shrinkage byconcentrated caustic alkali.

If aqueous solutions of the aforesaid compounds are employed, there mayalso be added to such compounds the water-soluble buffer salts of thealkalis or alkaline earths with weak acids. such as sodium acetate andsimilar compounds. By means of these additions, possible damage to thefiber, particularly at high temperatures is avoided. When operating athigher temperatures, the reaction between the textile material and thealphamethyl-halide derivatives is accelerated and may be satisfactorilycompleted for water-repellent purposes in a shorter time than wherelower temperatures are employed.

The following examples are illustrative and the invention is not to beconsidered as limited thereto except as indicated in the appendedclaims.

Examples for textile treatment 1. A fabric for wearing apparel made ofspun rayon (viscose) is passed through an aqueous solution whichcontains 20 grams per liter of a quaternary pyridinium compound of themethyl chloride derivative prepared from carbamic ester ofoctadecylalcohol CIBHS'IO.CO.NH2 trioxymethylene (CI-I20): and dryhydrogen chloride, as more specifically described hereinafter. The saidfabric is passed through the said aqueous solution while the latter isat about 35 C. Thereafter the impregnated material is dried andthereupon subjected to heat treatment in a drying chamber at about 95 C.for 5 hours.

2. Dyed cotton yarn is introduced at 50 C.

, into an aqueous solution of grams per liter of the quaternary pyridinecompound of the methyl chloride derivative prepared from stea- ,roylurea Ci'7I'L'l5.C0-NH.CO.NH2 trioxymethylene solution while the latteris at about 40 C. Thereafter the impregnated material is dried andthereupon subjected to heat treatment in a drying chamber at about 85 C.for 6 hours.

4. Cotton calico is passed through an aqueous solution which contains 15grams per liter of a quaternary pyridinium compound of the methylchloride derivative prepared from stearic acid hydrazideC1'lHa5.CO.NH.NH2 trioxymethylene (CH-i0): and dry hydrogen chloride; asmore specifically described hereinafter. The said 'fabric is passedthrough the said aqueous solution while the latter is at about 40 C.Thereafter the impregnated material is dried and thereupon subjected toheat treatment in a drying chamber at about 85 C. for 6 hours.

5. A plush fabric, consisting of cotton in warp and weft an artificialsilk spun fiber in the pile, is passed through an aqueousbath whichcontains per liter 250 grams of 9, formaldehydeurea condensation productwhich is on the market under the name Kaurit," 6 grams of primary sodiumphosphate. 6 grams of secondary sodium phosphate, 2 grams of tartaricacid, and 15 grams of the quaternary pyridine salt obtained by doubledecomposition of pyridine with the methyl chloride compound formed fromcarbamic ester of octadecylalcohol C1aH3'iO.CO.NI-Iz trioxymethylene(CI-I); and dry hydrogen chloride, as more specifically describedhereinafter. The said fabric is passed through the said aqueous solutionwhile the latter is about C. Thereafter the impregnated material issqueezed out,

brushed, and dried. The material is subjected to a heat treatment in adrying chamber at about 120 C. for 2 hours, then.

Ez'ramples for chemicals pyridinium salt of the methyl chloridederivative.

of carbamic ester of octadecylalcohol is formed having the formula:

(115E310 C O.NH.CH1.N.C1

7. Into a mixture, at a temperature of about 20 C., of 327 grams ofstearoyl urea 1500 grams of benzene, and 60 grams of trioxymethylene,dry hydrochloric acid gas is introduced until the formation of themethyl chloride compound takes place. This compound is treated as statedin Example 6 and is stirred with grams of pyridine at room temperature.The quaternary pyridinium salt of the methyl chloride derivativeof'stearoyl urea is formed having the formula:

8. Into a mixture, at a temperature of about 20 C. of 356 grams ofallophanic octadecylester C1aHJ'IO.CO.NH.CO.NH2 (Liebigs Annalen derChemie 244, 41), 2000 grams of benzene, and 60 grams trioxymethylene,dry hydrochloric acid gas is introduced until the formation of themethyl chloride compound takes place. This compound is treated as statedin Example 6 and is stirred with 100 grams of pyridine at roomtemperature. The quaternary pyridinium salt of the methyl chloridederivative of allophanic octadecylester is formed having the formula:

The above methyl chloride compounds without pyridine may be employed inbenzene or like solvent to treat textiles in a manner similar to thatset forth in Examples 1 to 5. The conversion of the other materialsgiven below for the production of chemicals and the use of suchchemicals in the form of their alpha methyl halide compounds is effectedin the same manner as given in the above examples. The other substancesreferred to are as follows:

stearo-hydroxamic acid C17Ha5.CO.N.HOH

and derivatives of urea, thiourea, or dimethylolurea which contain. analiphatic radical of at least ten carbon atoms, for example:

N-n-heptadecyl-urea Cl'IH3li.NH.CO-NHI r stearoyl-thioureaCl'1Has.CO.NH.CS.NH2 or allophanlc ester thiourea, for examplecurnaoconncsmn The amount of the reaction product deposited whenuncombined with a tertiary amine in Examples l to on the textilematerial will naturally vary with the weight of the material and itsreactability. I have found that, ordinarily an amount equal to 0.5-1.5per cent of the material is sufllclent to give the effect. When combinedto form a quaternary ammonium salt, approximately 1-2 per cent, based onthe weight of the material will give the desired eifect. The textilesproduced in accordance with the above examples show a high degree ofwater-repellence. The fibers of the textiles have a superficialetheriilcation. They show improved properties with respect to knowntextiles treated with fatty acid anhydrides including greater durabilitytowards dry-cleaning with benzene and soap washing. The feel and hang ofthe material having waterrepellence as produced above is notsubstantially altered. In additio', the artificial silks have-resistance to swelling agents and wetting agents.

simple apparatus at relatively small expense.

The term "halogen" as used in the appended claims is intended to includehalogen elements, such as chlorine or bromine.

The expression textile material" used herein is intended to coverfibers, yarns, fabrics including velvet; and other pile fabrics, orother forms of cotton, Jute, linen, hemp 0r rayon, including viscose,cuprammonium or other precipitated cellulose or derivatives of cellulosesuch as acetyl cellulose and animal fiber such as for example wool.

While the invention has been described in detail according to thepreferred manner of carrying out the process, it will be obvious tothose skilled in the art, after understanding the invenquinoline, or anN-alkyl-piperidine ortion. that changes and modifications may be madetherein without departing from the spirit or scope of the invention, andit is intended in "the appended claims to cover all such changes andmodiiications.

What is claimed as new and desired to be secured by Letters Patent is:

1. A process for rendering textile material water-repellent whichcomprises heating the material with a compound of the formulaR.Y.CH:.I-Ialogen where R is an aliphatic radical containing at least 10carbon atoms from the group consisting of NH.CO.NH,

CO.NHCONH, CONHNH, CO.NHCSNH.

O.C0.NH, O.CO.NHCONH, O.CONHCSNH, and CO.NHO, to render itwater-repellent.

2. A process for rendering textile material watext-repellent whichcomprises impregnating the material with a compound of the formula whereR is an aliphatic radical containing at least 10 carbon atoms. and thenheating the impregnated material in the absence of moisture untilitbecomes water-repellent.

3. A process for rendering textile material water-repellent whichcomprises impregnating the material with a compound of the formulaR.CO.NH.CO.NH.CH:.C1

where R is an aliphatic radical containing at least 10 carbon atoms, andthen heating the impregnated material in the absence of moisture untilit becomes water-repellent.

4. A process for rendering textile material water-repellent whichcomprises impregnating the material with a compound of the formulaR.O.CO.NH.CO.NH.CH:.CI

where R. is an aliphatic radical containing at least 10 carbon atoms,and then heating the impregnated material in the absence of moistureuntil it becomes water-repellent.

5 A process according to claim 2 in which the compound employed forimpregnation has the 6. A process according to claim 3 in which thecompound employed for impregnation has the formulaCi1Has.CO.NH.CO.NH.CHa-.Cl

CisI'Is'1.O.CO.NH.CO.NH.CH:.C1

ERNST WALTMANN. EDGAR WOLF.

and Y is a radical selected

